JPWO2017033916A1 - Unstretched film and molded body - Google Patents

Abstract

A first film, a second film, and a third film, each including at least one polyester resin, wherein the second film includes the first film and the third film; A non-stretched film in which at least the second film includes a glycol-modified polyethylene terephthalate resin and has a total thickness of 10 μm or more.

Description

The present invention relates to an unstretched film and a molded body.
This application claims priority on August 24, 2015 based on Japanese Patent Application No. 2015-164617 for which it applied to Japan, and uses the content for it here.

Various resins have been studied as materials for laminating films and forming films.
Among these, polyester resins are generally used because they are excellent in mechanical properties and chemical properties.

  For example, Patent Document 1 discloses a film for laminating, which includes polyethylene terephthalate (hereinafter sometimes referred to as “PET”). In patent document 1, mechanical strength and heat resistance are improved by performing a biaxial stretching process to a film.

  Also, for example, Patent Document 2 is a laminated film for a design material such as an interior / exterior panel, in which 50 layers or more of layers made of polyester resin A and layers made of polyester resin B are alternately laminated. A biaxially stretched film is disclosed.

JP 2009-006543 A JP 2010-184493 A

  However, the film disclosed in Patent Document 1 has a problem that it is inferior in heat sealability and molding processability because the film is stretched.

  The present invention has been made in view of the above circumstances, and can be heat-sealed under a wide range of temperature conditions and is excellent in molding processability, and molding obtained by subjecting it to secondary processing. The challenge is to provide a body.

As a result of intensive studies to solve the above problems, the present invention including the following embodiments has been completed.
[1] having at least one or more polyester resins, a first film, a second film, and a third film;
The second film is configured by being laminated between the first film and the third film,
At least the second film includes a glycol-modified polyethylene terephthalate resin,
An unstretched film having a total thickness of 10 μm or more.

[2] The unstretched film according to [1], wherein the polyester resin is any one of a polyethylene terephthalate resin, a polybutylene terephthalate resin, and a copolymerized polyethylene terephthalate resin.

[3] The unstretched film according to [1] or [2], which exhibits a softening point at 30 ° C. or higher and 100 ° C. or lower.

[4] The polyester resin includes a polyethylene terephthalate resin,
[1] to [3], wherein the unstretched films show seal strength at a seal temperature of 110 ° C. or higher under a seal time of 1 second and a seal pressure of 0.1 MPa, and the seal strength is 1 N / 15 mm or higher. ] The unstretched film as described in any one of.

[5] The polyester resin includes a polybutylene terephthalate resin. The unstretched films are sealed at a seal temperature of 1 second and a seal pressure of 0.1 MPa. / The unstretched film according to any one of [1] to [3], which is at least 15 mm.

[6] The unstretched film according to any one of [1] to [5], wherein the elongation at break at 100 ° C. is 200% or more.

[7] The first film is laminated so as to be one outermost layer,
The unstretched film according to [1], wherein the third film is laminated so as to be the other outermost layer.

[8] The unstretched film according to [7], wherein a content ratio of the glycol-modified polyethylene terephthalate resin in the second film is higher than a content ratio in the first film and a content ratio in the third film. the film.

[9] The content ratio of the glycol-modified polyethylene terephthalate resin in the first film is 1 to 20% by mass, and the content ratio of the glycol-modified polyethylene terephthalate resin in the second film and the third film is 5 The unstretched film according to [8], which is ˜40 mass%.

[10] A molded body obtained by subjecting the unstretched film according to [1] to secondary processing.

  The unstretched film of the present invention has at least two layers containing at least one polyester resin and has a total thickness of 10 μm or more, and thus can be heat-sealed under a wide range of temperature conditions and molded. Excellent in properties.

  Moreover, since the molded object of this invention is obtained by carrying out the secondary process of the said unstretched film, it can shape | mold easily.

It is sectional drawing which shows the structure of the unstretched film which is one Embodiment to which this invention is applied. The result of the dynamic viscoelasticity test of each film produced in Examples 1 and 2 and Comparative Example 1 is shown.

  Hereinafter, the unstretched film which is one embodiment to which the present invention is applied, and a molded body obtained by secondary processing of the film will be described in detail. In the drawings used in the following description, in order to make the features easy to understand, the portions that become the features may be shown in an enlarged manner for convenience, and the dimensional ratios of the respective components are not always the same as the actual ones.

<Unstretched film>
First, the structure of the unstretched film which is one embodiment to which the present invention is applied will be described. FIG. 1 is a schematic cross-sectional view of an unstretched film 1 that is an embodiment to which the present invention is applied. As shown in FIG. 1, the unstretched film 1 of this embodiment is a laminated film composed of three layers, and includes a first film 2, a second film 3, and a third film 4. It is roughly structured.

  In the present embodiment, the unstretched film 1 composed of three layers will be described, but it is not particularly limited as long as it is two or more layers.

  The unstretched film 1 can be used for laminating applications such as functional sealants and molding applications such as deep drawing molding and insert molding.

  In the unstretched film 1 of the present embodiment, the second film 3 is inserted between the first film 2 and the third film 4, and the first film 2 and the third film 4 are the outermost layers. Are stacked.

  Moreover, the unstretched film 1 of this embodiment is a film which has not been stretched in the manufacturing process. By not performing the stretching treatment, heat sealing is possible under a wide range of temperature conditions, and the moldability is excellent.

  The 1st film 2, the 2nd film 3, and the 3rd film 4 contain at least 1 or more polyester resin.

  The polyester resin is a polymer composed of a dicarboxylic acid component and a glycol component. Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfone dicarboxylic acid, and diphenoxyethanedicarboxylic acid. , Aromatic dicarboxylic acids such as 5-sodium sulfoisophthalic acid and phthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, fatty acid such as fumaric acid, and fat such as cyclohexanedicarboxylic acid Examples thereof include cyclic dicarboxylic acids and oxycarboxylic acids such as p-oxybenzoic acid. Of these dicarboxylic acid components, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid are preferred. On the other hand, examples of the glycol component include aliphatic glycols such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, and neopentylglycol, alicyclic glycols such as cyclohexanedimethanol, bisphenol A, and bisphenol S. Examples thereof include polyoxyethylene glycols such as aromatic glycol, diethylene glycol, and polyethylene glycol. Of these glycol components, ethylene glycol is preferred. These dicarboxylic acid components and glycol components may be used alone or in combination of two or more.

  The polyester resin is not particularly limited as long as it is a polymer composed of the dicarboxylic acid component and the glycol component. Specifically, for example, a PET resin, a polybutylene terephthalate (hereinafter sometimes referred to as “PBT”) resin, a glycol-modified polyethylene terephthalate (hereinafter referred to as “PETG”) which is a copolymerized polyethylene terephthalate resin. A) resin.

By selecting a PET resin as the polyester resin, the sealing property and moldability of the unstretched film 1 can be improved.
Moreover, the heat resistance of the unstretched film 1 can be improved by selecting a PBT resin as the polyester resin.
Moreover, by using PETG resin as the polyester resin in combination with PET resin or PBT resin, crystallization of the PET resin or PBT resin can be suppressed, and the brittleness of the unstretched film 1 can be improved.

  The content ratio of the PETG resin contained in each film of the first film 2, the second film 3, and the third film 4 may be the same or different in each film. Moreover, the content rate of PETG resin can be suitably set with the kind of polyester resin (except PETG resin) contained in each film, and the use of the unstretched film 1.

  For example, when a PET resin is included in each film constituting the unstretched film 1, only the second film 3 may contain the PETG resin. At this time, it is preferable that the content rate of PETG resin is 1-40 mass% with respect to the mass of the 2nd film 3, and it is more preferable that it is 5-20 mass%.

  In the 2nd film 3, the brittleness of the 2nd film 3 can be improved because the content rate of PETG resin is 1 mass% or more. Moreover, the rigidity of a film can be maintained because the content rate of PETG resin is 40 mass% or less.

  In addition, for example, when the PBT resin is included in each film constituting the unstretched film 1 and the unstretched film 1 is used for laminating the first film 2 side to the adherend, the content ratio of the PETG resin However, in the 1st film 2 which is a surface which contacts a to-be-adhered body, it is preferable that it is 1-20 mass%, and it is more preferable that it is 5-10 mass%. Moreover, in the 2nd film 3 and the 3rd film 4, it is preferable that it is 5-40 mass%, and it is more preferable that it is 10-30 mass%.

  In the 2nd film 3 and the 3rd film 4, the brittleness of the 2nd film 3 and the 3rd film 4 can be improved because the content rate of PETG resin is 5 mass% or more. Moreover, the heat resistance of a film can be maintained because the content rate of PETG resin is 40 mass% or less. Moreover, in the 1st film 2, the solvent resistance and adhesiveness with a to-be-adhered body are securable by reducing the content rate of PETG resin rather than the 2nd film 3 and the 3rd film 4. FIG.

  The first film 2 and the third film 4 include an antioxidant, an antistatic agent, a crystal nucleating agent, inorganic particles, organic particles, a thinning agent, a thickening agent, a heat stabilizer, a lubricant, and an infrared absorber. A master batch such as an ultraviolet absorber (hereinafter sometimes referred to as “MB”) may be added. Thereby, the slip of the unstretched film 1 can be improved and troubles, such as a wrinkle entering at the time of manufacture, can be prevented.

  Although it does not specifically limit as addition amount of MB, Specifically, 1-5 mass% is preferable with respect to each film of the 1st film 2 or the 3rd film 4, for example.

The thickness of the first and third films is preferably 1 to 10 μm. Moreover, it is preferable that the thickness of a 2nd film is 10-100 micrometers.
Specifically, the total thickness of the unstretched film 1 of the present embodiment is, for example, preferably 10 to 1000 μm, more preferably 20 to 500 μm, and particularly preferably 20 to 300 μm. The total thickness of the unstretched film 1 is preferably 10 μm or more and 1000 μm or less.

  The unstretched film 1 of this embodiment can be heat-sealed under a wide temperature condition by not performing the stretching treatment. Specifically, for example, when a PET resin is selected as the polyester resin contained in the first film 2, the second film 3, and the third film 4, the unstretched films 1 are sealed for 1 second, When heat sealing is performed under conditions of a seal pressure of 0.1 MPa, the seal strength is shown at a seal temperature of 110 ° C. or higher, and the seal strength at this time is preferably 1 N / 15 mm or more, and preferably 5 N / 15 mm or more. More preferred.

  Also, for example, when a PBT resin is selected as the polyester resin contained in the first film 2, the second film 3, and the third film 4, the unstretched films 1 are sealed with each other for a sealing time of 1 second and a sealing pressure of 0. When heat-sealed under a condition of 1 MPa, the sealing strength is exhibited at a sealing temperature of 210 ° C. or higher, and the sealing strength at this time is preferably 1 N / 15 mm or more, and more preferably 2 N / 15 mm or more.

  The seal strength can be measured by measuring the seal strength at a seal width of 15 mm using a tensile tester (for example, TENSILON RTG-1310 manufactured by A & D Corporation).

The unstretched film 1 of the present embodiment is excellent in molding processability because it has a low softening point and a high elongation at break by not being stretched.
As a softening point of the unstretched film 1 of this embodiment, specifically, it exists in the range of 30-100 degreeC, for example, and it exists more preferably in the range of 40-90 degreeC.

  The softening point can be measured using a dynamic viscoelasticity measuring apparatus (for example, EXSTAR6000 manufactured by Seiko Instruments Inc.).

  In addition, as the breaking elongation of the unstretched film 1 of the present embodiment, specifically, for example, the breaking elongation at 100 ° C. is preferably 200% or more.

  The elongation at break can be measured according to the method described in JIS Z7127 using an autograph apparatus (for example, AUTOGRAPH AGS-X manufactured by Shimadzu Corporation).

<Method for producing unstretched film>
Next, the manufacturing method of the unstretched film 1 mentioned above is demonstrated.
The unstretched film 1 of the present embodiment is the same as the first film 2, the second film 3, and the third film 4 described above, for example, an air-cooled or water-cooled coextrusion inflation method, a coextrusion T die. You may manufacture by the method of forming into a film by the method. Among these methods, the method of forming a film by the coextrusion T-die method is excellent from the viewpoint of controlling the thickness of each layer. The unstretched film 1 of the present embodiment is not subjected to a stretching process in the manufacturing process. In addition, the unstretched film 1 of the present embodiment is manufactured by separately manufacturing the above-described first film 2, the second film 3, and the third film 4 and then joining them with a laminator or the like. Also good.

<Molded body>
The molded body of the present embodiment is obtained by subjecting the unstretched film 1 described above to secondary processing.
Specifically as a molded object of this embodiment, when the unstretched film 1 is used for a lamination use, a functional sealant etc. are mentioned, for example. In addition, for example, when the unstretched film 1 is used for molding applications, examples thereof include deep drawing molding applications and insert molding applications. Since the molded body of the present embodiment is obtained by subjecting the above-described unstretched film 1 to secondary processing, it can be easily molded.

  As described above, according to the unstretched film 1 of the present embodiment, since it has at least two layers including at least one polyester resin and the total thickness is 10 μm or more, it can be heated under a wide temperature condition. It can be sealed and has excellent moldability.

  Moreover, according to the unstretched film 1 of this embodiment, it has the 1st film 2, the 2nd film 3, and the 3rd film 4, and the 2nd film 3 is a 1st film. 2 and the third film 4, and at least the second film 3 contains a PETG resin, and the content ratio of the PETG resin in the second film 3 is the first film. Since it is higher than the content ratio in 2 and the content ratio in the third film 4, for example, the brittleness can be improved while ensuring rigidity on the surface of the unstretched film 1.

  Moreover, since the molded object of this embodiment is obtained by carrying out the secondary process of the said unstretched film 1, it can shape | mold easily.

  The embodiment of the present invention has been described in detail with reference to the drawings. However, the specific configuration is not limited to this embodiment, and includes designs and the like that do not depart from the gist of the present invention. For example, in the unstretched film 1 described above, an example composed of three layers including a polyester resin has been described. However, a layer having another function may be newly provided between the layers or on the outermost layer.

  Hereinafter, although the effect of the present invention is explained in detail using an example and a comparative example, the present invention is not limited to the following example.

<Preparation of unstretched film>
Example 1
As a polyester resin contained in the first film, the second film, and the third film, a PET resin (made by Mitsubishi Chemical Corporation, brand: GM700Z) was prepared. Further, PETG resin (manufactured by SK-Chemical Co., brand: S2008) was further prepared as a polyester resin contained in the second film. The glycol component in the PETG resin is ethylene glycol.

  Next, a PET film as a first film, a resin composition in which PET resin and PETG resin are mixed as a second film, and a PET resin as a third film are coextruded in this order, and a laminated film Was made. At that time, in the second film, the mixing ratio was adjusted so that the PET resin was 93% by mass and the PETG resin was 7% by mass. The produced laminated film was used as an unstretched film.

  The thickness of the first film was 3 μm, the thickness of the second film was 24 μm, the thickness of the third film was 3 μm, and the total thickness of the unstretched film was 30 μm.

(Example 2)
PBT resin (Mitsubishi Engineering Plastics, brand: 5020) and PETG resin (SK-Chemical, brand: S2008) are used as the polyester resin contained in the first film, the second film, and the third film. Prepared.

  Next, a resin composition in which PBT resin and PETG resin are mixed as the first film, a resin composition in which PBT resin and PETG resin are mixed as the second film, and PBT resin and PETG resin as the third film The mixed resin composition was coextruded in this order to produce a laminated film. At that time, in the first film, the PBT resin is 93% by mass and the PETG resin is 7% by mass, in the second film, the PBT resin is 80% by mass, the PETG resin is 20% by mass, and in the third film, The mixing ratio was adjusted so that the PBT resin was 82% by mass and the PETG resin was 18% by mass. The produced laminated film was used as an unstretched film.

  The thickness of the first film was 2 μm, the thickness of the second film was 14 μm, the thickness of the third film was 4 μm, and the total thickness of the unstretched film was 20 μm.

(Comparative Example 1)
As Comparative Example 1, a commercially available biaxially stretched PET film (manufactured by Toyobo Co., Ltd., brand: E5107) was prepared.
The total thickness of the biaxially stretched film was 25 μm.

<Evaluation of heat sealability>
The heat-sealability of the unstretched film prepared in Example 1 and the biaxially stretched film prepared in Comparative Example 1 was evaluated. The heat sealability was evaluated for the same film heat-sealed. The heat sealing conditions were a sealing temperature of 110 to 180 ° C., a sealing time of 1 second, and a sealing pressure of 0.1 MPa. The heat sealability was evaluated by measuring the seal strength at a seal width of 15 mm using a tensile tester (manufactured by A & D Co., Ltd., TENSILON RTG-1310).

  Table 1 shows the seal strength when sealed at each seal temperature.

  As shown in Table 1, the unstretched film of Example 1 showed seal strength at a seal temperature of 110 ° C. or higher, whereas the biaxially stretched film of Comparative Example 1 had a seal temperature of 180 ° C. It did not show seal strength.

  Next, the heat-sealability was similarly evaluated for the unstretched film prepared in Example 2 and the biaxially stretched film prepared in Comparative Example 1. The heat sealing conditions were a sealing temperature of 210 to 240 ° C., a sealing time of 1 second, and a sealing pressure of 0.1 MPa.

  Table 2 shows the seal strength when sealed at each seal temperature.

  As shown in Table 2, the unstretched film of Example 2 showed seal strength at a seal temperature of 210 ° C. or higher, whereas the biaxially stretched film of Comparative Example 1 showed seal strength at a seal temperature of 210 ° C. There wasn't.

  From the above results, it was confirmed that the unstretched films of Examples 1 and 2 can be heat-sealed even at low temperatures and can be heat-sealed under a wide temperature condition.

<Measurement of softening point>
The softening point of the unstretched film prepared in Examples 1 and 2 and the biaxially stretched film prepared in Comparative Example 1 were measured. The measurement of the softening point was performed using a dynamic viscoelasticity measuring apparatus (manufactured by Seiko Instruments Inc., EXSTAR6000).

  In FIG. 2, the result of the dynamic viscoelasticity test of each film is shown. In FIG. 2, the temperature at which the elastic modulus sharply decreased was taken as the softening point. From the results of the dynamic viscoelasticity test, the softening point of the unstretched film of Example 1 is about 90 ° C., the softening point of the unstretched film of Example 2 is about 50 ° C., and the biaxial stretching of Comparative Example 1 It was confirmed that the softening point of the film was about 140 ° C. Thus, the softening point of Examples 1 and 2 existed in the range of 30-100 degreeC.

  The softening point was the temperature at which the value of the elastic modulus of the film was greatly reduced. On the other hand, in the biaxially stretched film, there is no clear softening point, and the elastic modulus gradually decreases. Therefore, the temperature when the number of digits of the elastic modulus changed was taken as the softening point.

<Measurement of elongation at break>
The unstretched film produced in Examples 1 and 2 and the biaxially stretched film produced in Comparative Example 1 were measured for breakage. The elongation at break was measured according to the method described in JIS Z7127 using an autograph apparatus (for example, AUTOGRAPH AGS-X manufactured by Shimadzu Corporation). The elongation at break was measured at 23 ° C. and 100 ° C. in two directions, the MD direction and the TD direction.

  Table 3 shows the elongation at break of each film at 23 ° C and 100 ° C.

  As shown in Table 3, the unstretched films of Examples 1 and 2 have a breaking elongation at 100 ° C. of 500% or more, whereas the biaxially stretched film of Comparative Example 1 has a breaking elongation of 200 at 100 ° C. % Or less.

  From the above results, it was confirmed that the unstretched films of Examples 1 and 2 were excellent in moldability because the softening point was low and the elongation at break was high.

  The unstretched film of the present invention can be heat-sealed under a wide range of temperature conditions and is excellent in molding processability, so it can be used for lamination applications such as functional sealants, and molding applications such as deep drawing and insert molding. There is.

DESCRIPTION OF SYMBOLS 1 Unstretched film 2 1st film 3 2nd film 4 3rd film

As a result of intensive studies to solve the above problems, the present invention including the following embodiments has been completed.
[1] having at least one or more polyester resins, a first film, a second film, and a third film;
The second film is configured by being laminated between the first film and the third film,
At least the second film includes a glycol-modified polyethylene terephthalate resin,
Total thickness Ri der more than 10μm,
The first film is laminated so as to be one outermost layer,
The third film is laminated so as to be the other outermost layer,
The content ratio of the glycol-modified polyethylene terephthalate resin in the second film is higher than the content ratio in the first film and the content ratio in the third film,
The content of the glycol-modified polyethylene terephthalate resin in the first film is 1 to 20% by mass, and the content of the glycol-modified polyethylene terephthalate resin in the second film and the third film is 5 to 40% by mass. %
An unstretched film, wherein the polyester resin comprises a polybutylene terephthalate resin .

[ 2 ] The unstretched film according to [1 ] , which exhibits a softening point at 30 ° C or higher and 100 ° C or lower.

[3] before Symbol unstretched film between the sealing time of 1 second, under the conditions of sealing pressure 0.1 MPa, shows a seal strength at sealing temperature 210 ° C. or higher, the sealing strength is 1N / 15 mm or more, the [1 ] Or an unstretched film according to [2] .

[ 4 ] The unstretched film according to any one of [1] to [ 3 ], wherein the elongation at break at 100 ° C. is 200% or more.

[ 5 ] A molded body obtained by secondary processing the unstretched film according to [1].

Claims (10)

A first film, a second film, and a third film, each including at least one polyester resin;
The second film is configured by being laminated between the first film and the third film,
At least the second film includes a glycol-modified polyethylene terephthalate resin,
An unstretched film having a total thickness of 10 μm or more.   The unstretched film according to claim 1, wherein the polyester resin is any one of a polyethylene terephthalate resin, a polybutylene terephthalate resin, and a copolymerized polyethylene terephthalate resin.   The unstretched film of Claim 1 or 2 which shows a softening point at 30 degreeC or more and 100 degrees C or less. The polyester resin includes a polyethylene terephthalate resin,
The unstretched film is sealed at a seal temperature of 110 ° C or higher under a seal time of 1 second and a seal pressure of 0.1 MPa, and the seal strength is 1 N / 15 mm or higher. The unstretched film according to claim 1. The polyester resin contains a polybutylene terephthalate resin. The unstretched films are sealed at a seal temperature of 1 second and a seal pressure of 0.1 MPa. The seal strength is 1 N / 15 mm or more. The unstretched film according to any one of claims 1 to 3, wherein   The unstretched film according to any one of claims 1 to 5, wherein the elongation at break at 100 ° C is 200% or more. The first film is laminated so as to be one outermost layer,
The unstretched film according to claim 1, wherein the third film is laminated so as to be the other outermost layer.   The unstretched film according to claim 7, wherein a content ratio of the glycol-modified polyethylene terephthalate resin in the second film is higher than a content ratio in the first film and a content ratio in the third film.   The content of the glycol-modified polyethylene terephthalate resin in the first film is 1 to 20% by mass, and the content of the glycol-modified polyethylene terephthalate resin in the second film and the third film is 5 to 40% by mass. The unstretched film according to claim 8, which is%.   The molded object obtained by carrying out secondary processing of the unstretched film of Claim 1.

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